CN101979346B - Comprehensive treatment method for high-concentration pesticide wastewater - Google Patents
Comprehensive treatment method for high-concentration pesticide wastewater Download PDFInfo
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Abstract
The invention provides a comprehensive treatment method for high-concentration pesticide wastewater. The pesticide wastewater generated in the pesticide synthesizing process is pretreated, and is treated by an integrated biochemical method combining two or three of a membrane biochemical reaction method, a three-phase fluidized reaction method and an aerobic biotreatment method until the COD of the wastewater is less than 100mg/L, and the wastewater is discharged. The effluent after the treatment of the comprehensive treatment method meets the grade 1 of the integrated wastewater discharge standard. According to the method, the high-concentration pesticide wastewater can be directly treated, the consumption of a great amount of dilution water is avoided, and the treated wastewater meets the standard before being discharged.
Description
Technical field
The present invention relates to a kind of high concentration agricultural chemical wastewater treatment method.
Background technology
The more waste water of the general generation of pesticide producing process, its popular feature is: 1) organic concentration is high; 2) the pollutant component complicacy contains a large amount of inorganic salt simultaneously; 3) be difficult to adopt conventional biodegradable material many, the waste water treatment difficulty is big.
Not end for pesticide wastewater is administered; Agricultural chemicals enterprise adopts simple physico-chemical pretreatment to add conventional biological treatment; All have the biochemical treatment apparatus of different scales, but because the defective that biochemical device itself exists, organic wastewater with high concentration generally need dilute 10～100 times of ability and get into biochemical treatment; Consume great amount of water resources, terminal waste discharge total amount is big simultaneously.Also have the anaerobic-aerobic of employing technology to handle in addition, but the anaerobic treatment process is high to water quality requirement, a little less than the shock-resistant ability, speed of response is slower, and the reaction times is longer, and the processing structures volume is big.There is the problem that processing efficiency is low, facility investment big, the tail end wastewater quantity discharged is big equally in entire treatment technology, the gas frowziness of Anaerobic processes generation simultaneously, and discharging needs secondary treatment, and this has also limited the use of anaerobic technique.
Membrane bioreactor (MBR) is a kind of novel water technology that is combined with biological processing unit by film separation unit, replaces second pond with membrane module and in bio-reactor, keeps the high reactivity sludge concentration to reduce the sewage treatment facility occupation of land.Compare with traditional biochemical water technology, MBR has following principal feature: COD is high in its water inlet, can reach 10000～40000/L, and processing efficiency is high, effluent quality is good; Facility compact, floor space are little; Easy realization is controlled automatically, operational management is simple, and sludge quantity produces and lacks.Since the eighties, this technology more and more comes into one's own, and becomes one of focus of research.At present membrane bioreactor has been applied to more than ten countries such as the U.S., Germany, France, Italy, Spain, Japan and Egypt, and existing large quantities of film separated activated sludge system is in operation.But its membrane module price is high, and facility investment is big, and its facility investment generally accounts for 50～70% of processing cost.Under the situation of handling organic wastewater with high concentration; Water outlet is 2000mg/L under the situation of clearance water inlet COD20000mg/L according to 90%; Can further reduce water outlet COD through prolonging the residence time, COD will reach still difficulty relatively of the discharging 100mg/L of country, and facility investment simultaneously further strengthens; The device processes ability reduces, and processing cost rises uneconomical.
It is under the condition that has free oxygen (molecular oxygen) to exist that aerobe is handled, and the aerobic degradation organism makes its stable, innoxious treatment process.Mikrobe utilizes the organic pollutant (is main with dissolved form and colloidal) that exists in the waste water, has carried out oxygen metabolism as nutrition source.The speed of response that aerobe is handled is very fast, and the required reaction times is shorter, so the processing structures volume is less, facility investment is little, and processing cost is low, and the foul smell that distributes in the treating processes is less.So, the organic waste water of present centering, lower concentration, BOD concentration adopts the aerobe facture basically less than the organic waste water of 500mg/L in other words, and processed waste water can reach 100mg/L.Agricultural chemicals waste water COD is generally more than 10000mg/L; The highlyest can reach more than the 100000mg/L; As adopt aerobic treatment process need add a large amount of dilution waters waste water COD is diluted to 500mg/L, so not only having wasted great amount of water resources has also increased terminal COD quantity discharged.
Three-phase fluid bed reactor is a kind of technology of biomembrance process, is on the basis of aerobic process, to adopt carrier appendix biology to be used for wastewater treatment.Obviously improved mass transfer characteristic through the appendix biotechnology; Improved the mass transfer behavior of oxygen in the wastewater biological aerobic treatment; The biooxidation reactions of a series of complicacies takes place in the microbial film in fluidized-bed on the porous support particle, finally makes the macromole organic matter in the waste water obtain efficient degradation.The common aerobic biochemical device of its water inlet COD concentration ratio is high; Generally can reach 1000～4000mg/L; Removing efficient can improve about 10～20%, but the COD of its water inlet still has big gap with present agricultural chemicals comprehensive wastewater COD, as adopts this art breading still to need 10～30 times dilution.
The present invention is under above-mentioned technical background; Characteristics to agricultural chemicals waste water propose a kind of treatment process, are the waste water of 10000～40000mg/L for COD, directly use Membrane Bioreactor for Wastewater Treatment; Treat effluent is used processing such as three-phase fluid bed reactor, aerobic biochemical pond more successively; Promote the degraded of macromolecular cpd through selecting for use of carrier in the three-phase fluidized bed, the final back water of handling can qualified discharge, and the treatment process that the present invention proposes has been avoided independent use three-phase fluid bed reactor, and (water inlet COD1000～4000mg/L), aerobic biochemical pond are (during water inlet COD500～600mg/L) to the Macrodilution of hc effluent; Reduce the use of Macrodilution water; Also solved to use and handled membrane bioreactor high concentration agricultural chemical waste water, the plant investment cost is big, and water outlet directly reaches the problem of the difficulty of discharging standards; Processed waste water can reach discharging standards, has obtained lower processing cost simultaneously.
Summary of the invention
The objective of the invention is to: a kind of integrated processing method of waste water is provided, makes it can be applicable to the processing of the agricultural chemicals synthetic wastewater of high density.
Above-mentioned purpose of the present invention realizes through following technical scheme:
A kind of integrated conduct method of agricultural chemicals waste water is provided; Be through after the pre-treatment with the agricultural chemicals waste water that produces in the agricultural chemicals building-up process; The integrated biochemical method that adopts two or three method in film biochemical reaction method, three-phase fluidization reaction method or the aerobic biological process for treating to be combined into is handled, and after waste water COD is lower than 100mg/L, discharges.
The high concentrated organic wastewater that described agricultural chemicals waste water produces for the pesticide producing process, its COD is at 15000～40000mg/L, and saltiness is at 2～25% (weight percents), and total nitrogen is at 50～1000mg/L.
Described integrated conduct method, preferred below several kinds of schemes:
The agricultural chemicals waste water that produces in the agricultural chemicals building-up process through after the pre-treatment, is handled with film biochemical reaction method earlier, handled with aerobic biological process for treating again, after waste water COD is lower than 100mg/L, discharge;
Or,
The agricultural chemicals waste water that produces in the agricultural chemicals building-up process through after the pre-treatment, is handled through film biochemical reaction method, three-phase fluidization reaction method and three kinds of methods of aerobic biological treatment successively, after waste water COD is lower than 100mg/L, discharged.
Described film biochemical reaction method is waste water to be got into the film biochemical reactor stopped 3～30 days;
Described three-phase fluidization negative side method is waste water to be got into the three-phase fluidization reactor drum stopped 12～40 hours;
Described aerobic biological process for treating is waste water to be got into the aerobic biochemical device stopped 20～30 hours.
Described integrated conduct method further preferably specifically may further comprise the steps:
1) agricultural chemicals waste water is carried out pre-treatment; Described pre-treatment is the combination of one or more treatment processs during neutralization, oil removal flocculation or evaporation are desalted;
2) adopt film biochemical reaction method to handle, be about to get into the film biochemical reactor, 3～30 days residence time, make the COD of water outlet reach 500～4000mg/L through the pretreated waste water of step 1);
Described film biochemical reactor can use external or built-in membrane module;
The membrane module material can be selected FM, polycarbonate, Vilaterm, Vestolen PP 7052, pvdf, tetrafluoroethylene or pottery;
Said material aperture can be 0.002～0.02 micron.
3) adopt the three-phase fluidization reaction method to handle, be about to through step 2) the water outlet of film biochemical reactor after handling get into three-phase fluid bed reactor, 12～30 hours residence time, make the COD of water outlet reach 300～1000mg/L;
Described three-phase fluidization reactor drum carrier can select to use light ceramic, activated carbon, sand carbon, urethane filler, polyacrylamide gel, Mierocrystalline cellulose, alginate calcium or Z 150PH.
4) adopt aerobic biological process for treating to handle, the water outlet that is about to after the three-phase fluid bed reactor of step 3) is handled gets into the aerobic biochemical device, and 20～30 hours residence time, the COD that makes water outlet is less than 100mg/L.
In the above-mentioned treatment process method, the described pretreatment technology of step 1) can be used according to waste water quality situation arbitrary combination, as long as can remove inorganic salt, the free organic phase in the waste water to greatest extent.
The described neutralization of step 1) is to regulate wastewater pH to reach 6.5～8.5; Preferably adding weight percent concentration according to the wastewater pH situation is that 30% hydrochloric acid or 30% liquid caustic soda are regulated.
The described oil removal flocculation of step 1) can be to divide oil-yielding stratum after waste water leaves standstill 2～6hr, simultaneously the water layer flocculate and clarify.
It can be that waste water gets into the quintuple effect evaporator evaporation that the described evaporation of step 1) is desalted.
Film biochemical reactor (MBR): film biochemical reactor technology organically combines membrane separation technique and biotechnology; Adopting ultra-filtration membrane will handle the back water outlet separates with active sludge; The settling process that ultrafiltration system has replaced traditional dependence gravity to be separated; Make active bio mud continuously reuse to bio-oxidation pond, make the microorganism concn that wherein keeps higher than traditional biochemical system (10～25g/L), make living weight keep activity and resistance preferably.Thereby improved the COD concentration of water inlet, COD concentration can reach more than the 40000mg/L, improves treatment capacity, and because self decomposing of high-concentration raw substrate concentration makes the mud generation reduce, therefore no longer needs special second pond.
The three-phase fluidization reactor drum: the three-phase fluidization reactor drum is the advantage combination with common activated sludge process and biomembrance process; And introduced the advanced fluidizer in the chemical plant; Thereby has a volumetric loading height; Biodegradation rate is fast, water inlet COD can reach 1000～4000mg/L, and the adsorption catalysis oxygenizement through carrier promotes that some difficult degradations are further handled than larger molecular organics in addition.Advantages such as it is little that device has floor space, and initial cost and working cost are low.
The aerobic biochemical pond: be to use at present a kind of comparatively widely biochemical treatment apparatus, it is good that it has an effluent quality, can reach national grade one discharge standard; The processing power advantages of higher; But exist load low, water inlet COD only can reach 500mg/L, and hc effluent needs could handle behind the thin up; Capital construction and working cost are higher, the shortcoming of complex management.
Integrated approach of the present invention is not held integrated membrane bioreaction induction method (MBR), three-phase fluidized bed reaction method and three kinds of treatment technologies of traditional aerobic biological process for treating in the treatment technology at agricultural chemicals waste water; Adopt modular design; Make organic wastewater with high concentration need not dilution and get final product direct biochemical treatment, COD finally reaches emission standard 100mg/L by 10000～40000mg/L → 500～4000mg/L → 300～1000mg/L; The membrane bioreactor influent concentration is high, contact bio-oxidation technology water outlet qualified discharge but utilize; Adopt the transition of three-phase fluidization biotechnology in membrane bioreactor water outlet under the water inlet COD condition with higher with contacting between the water inlet of bio-oxidation tradition biochemical technology; Can be with the direct final qualified discharge of biochemical treatment of the high-concentration waste water of COD10000～40000mg/L; Realized the low emission of agricultural chemicals waste water, calculated according to 500 tons of hc effluents/sky treatment scale and can reduce 18000 tons/day of dilution wastewater flow rates.Also make the facility investment and the energy consumption of wastewater treatment that bigger reduction is all arranged in addition.The processing efficiency that has solved present biochemical processing existence is low, the shortcoming that water loss is big.
Description of drawings
Fig. 1 is the schema through film biochemical reaction method, three-phase fluidization reaction method and three kinds of integrated processing waste water of method of aerobic biological treatment of the present invention.
Fig. 2 is the schema through film biochemical reaction method and two kinds of integrated processing waste water of method of aerobic biological treatment of the present invention.
Embodiment
Form with embodiment specifies technical scheme of the present invention and effect below, but the present invention is not limited to following examples, and embodiment 1 and 2 treatment scheme are as shown in Figure 1, and embodiment 3 and 4 treatment scheme are as shown in Figure 2.
The organic wastewater with high concentration of handling in the embodiment of the invention is the pesticide producing comprehensive wastewater of green hill plant area of Jiangsu Youshi Chemical Co., Ltd, COD=15000～40000mg/L, saltiness 2～25%, total nitrogen 50～1000mg/L.
The waste water that production plant produces is aggregated in the balancing tank, and the waste water after mixing carries out pre-treatment, neutralizes successively, oil removal flocculation, evaporation desalt, and the evaporation water outlet that obtains is intake as biochemical device.
Membrane bioreactor volume 300L uses external ceramic super-filtering film, three-phase fluidized bed volume 500L, uses activated carbon to be carrier, aerobic biochemical pool volume 200L.
Embodiment 1.
1) COD of waste water is 22000mg/L after the pre-treatment, and total nitrogen 150mg/L uses Membrane Bioreactor for Wastewater Treatment, flooding velocity 1.2L/hr, and 10 days residence time, aeration keeps dissolved oxygen to reach 1～3mg/L, and the COD of water outlet is at 2000～2200mg/L, total nitrogen 80mg/L.
2) waste water after the Membrane Bioreactor for Wastewater Treatment of step 1) uses three-phase fluidized bed to handle, flooding velocity 20L/hr, and 1 day residence time, aeration keeps dissolved oxygen to reach 2～6mg/L, and the COD of water outlet is at 450～700mg/L, total nitrogen 60mg/L.
3) waste water after step 2) three-phase fluidized bed is handled gets into the aerobic biochemical pond and handles, flooding velocity 8L/hr, and 1 day residence time, aeration keeps dissolved oxygen to reach 2～6mg/L, and the COD of water outlet is at 80～100mg/L, total nitrogen 40mg/L.
Embodiment 2.
1) COD of waste water is 12000mg/L after the pre-treatment, and total nitrogen 80mg/L uses Membrane Bioreactor for Wastewater Treatment, flooding velocity 1.2L/hr, and 10 days residence time, aeration keeps dissolved oxygen to reach 1～3mg/L, and the COD of water outlet is at 1000～1500mg/L, total nitrogen 50mg/L.
2) waste water after the Membrane Bioreactor for Wastewater Treatment of step 1) uses three-phase fluidized bed to handle, flooding velocity 20L/hr, and 1 day residence time, aeration keeps dissolved oxygen to reach 2～6mg/L, and the COD of water outlet is at 300～500mg/L, total nitrogen 35mg/L.
3) waste water after step 2) three-phase fluidized bed is handled gets into the aerobic biochemical pond and handles, flooding velocity 8L/hr, and 1 day residence time, aeration keeps dissolved oxygen to reach 2～6mg/L, and the COD of water outlet is at 70～100mg/L, total nitrogen 20mg/L.
Embodiment 3.
1) COD of waste water is 22000mg/L after the pre-treatment, and total nitrogen 150mg/L uses Membrane Bioreactor for Wastewater Treatment, flooding velocity 1.2L/hr, and 10 days residence time, aeration keeps dissolved oxygen to reach 1～3mg/L, and the COD of water outlet is at 2000～2200mg/L, total nitrogen 80mg/L.
2) waste water after the Membrane Bioreactor for Wastewater Treatment of step 1) adds 1.5 times of water dilution back and gets into the aerobic biochemical ponds and handle, flooding velocity 8L/hr, and 1 day residence time, aeration keeps dissolved oxygen to reach 2～6mg/L, and the COD of water outlet is at 80～110mg/L, total nitrogen 40mg/L.
Embodiment 4.
1) COD of waste water is 15000mg/L after the pre-treatment, and total nitrogen 80mg/L uses Membrane Bioreactor for Wastewater Treatment, flooding velocity 1.2L/hr, and 10 days residence time, aeration keeps dissolved oxygen to reach 1～3mg/L, and the COD of water outlet is at 600～800mg/L, total nitrogen 50mg/L.
2) waste water after the Membrane Bioreactor for Wastewater Treatment of step 1) gets into the aerobic biochemical pond and handles, flooding velocity 8L/hr, and 1 day residence time, aeration keeps dissolved oxygen to reach 2～6mg/L, and the COD of water outlet is at 80～100mg/L, total nitrogen 20mg/L.
Comparative Examples 1.
The COD of waste water is 22000mg/L after the pre-treatment, total nitrogen 150mg/L, 40 times of thin ups; COD is 550mg/L, and total nitrogen 4mg/L uses the aerobic biochemical pond to handle; Flooding velocity 8L/hr, 1 day residence time, aeration keeps dissolved oxygen to reach 2～6mg/L; The COD of water outlet is at 80～120mg/L, total nitrogen 3mg/L.
Comparative Examples 2.
The COD of waste water is 22000mg/L after the pre-treatment, and total nitrogen 150mg/L uses Membrane Bioreactor for Wastewater Treatment, flooding velocity 1.2L/hr, and 10 days residence time, aeration keeps dissolved oxygen to reach 1～3mg/L, and the COD of water outlet is at 2000～2200mg/L, total nitrogen 80mg/L.
Comparative Examples 3.
The COD of waste water is 22000mg/L after the pre-treatment, and total nitrogen 150mg/L uses Membrane Bioreactor for Wastewater Treatment, flooding velocity 0.4L/hr, and 30 days residence time, aeration keeps dissolved oxygen to reach 1～3mg/L, and the COD of water outlet is at 800～1200mg/L, total nitrogen 60mg/L.
Comparative Examples 4.
The COD of waste water is 22000mg/L after the pre-treatment, total nitrogen 150mg/L, 10 times of thin ups; COD is 2200mg/L, and total nitrogen 15mg/L uses three-phase fluidized bed to handle; Flooding velocity 20L/hr, 1 day residence time, aeration keeps dissolved oxygen to reach 2～6mg/L; The COD of water outlet is at 400～600mg/L, total nitrogen 12mg/L.
Comparison through above embodiment and Comparative Examples can be found out; Adopt integrated approach of the present invention to handle the direct processing that the agricultural chemicals synthetic wastewater can be realized high dense agricultural chemicals waste water; Avoided the use of Macrodilution water, environmental protection more economically, the while has also been realized the qualified discharge of processed waste water.
Claims (4)
1. the integrated conduct method of an agricultural chemicals waste water; Be through after the pre-treatment with the agricultural chemicals waste water that produces in the agricultural chemicals building-up process; The integrated biochemical method that adopts film biochemical reaction method, three-phase fluidization reaction method and three kinds of methods of aerobic biological process for treating to be combined into is handled, and after waste water COD is lower than 100mg/L, discharges; Described integrated conduct method specifically may further comprise the steps:
1) agricultural chemicals waste water is carried out pre-treatment; Described pre-treatment is the combination of one or more treatment processs during neutralization, oil removal flocculation or evaporation are desalted;
2) adopt film biochemical reaction method to handle, be about to get into the film biochemical reactor, 3～30 days residence time, make the COD of water outlet reach 500～4000mg/L through the pretreated waste water of step 1);
3) adopt the three-phase fluidization reaction method to handle, be about to through step 2) the water outlet of film biochemical reactor after handling get into three-phase fluid bed reactor, 12～30 hours residence time, make the COD of water outlet reach 300～1000mg/L;
4) adopt aerobic biological process for treating to handle, the water outlet that is about to after the three-phase fluid bed reactor of step 3) is handled gets into the aerobic biochemical device, and 20～30 hours residence time, the COD that makes water outlet is less than 100mg/L.
2. the described integrated conduct method of claim 1; It is characterized in that: the high concentrated organic wastewater that described agricultural chemicals waste water produces for the pesticide producing process; Its COD is at 15000～40000mg/L, and saltiness is at 2～25% weight percents, and total nitrogen content is at 50～1000mg/L.
3. the described integrated conduct method of claim 1 is characterized in that: step 2) the external or built-in membrane module of described film biochemical reactor use; Described membrane module material is selected from FM, polycarbonate, Vilaterm, Vestolen PP 7052, pvdf, tetrafluoroethylene or pottery; Described membrane module material aperture is 0.002～0.02 micron.
4. the described integrated conduct method of claim 1, it is characterized in that: the described three-phase fluidization reactor drum of step 3) carrier is selected from light ceramic, activated carbon, sand carbon, urethane filler, polyacrylamide gel, Mierocrystalline cellulose, alginate calcium or Z 150PH.
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Inventor after: Qi Mingzhu Inventor after: Wang Dongchao Inventor after: Li Anming Inventor after: He Hongjun Inventor after: Xiong Suyi Inventor after: Tang Dinglong Inventor after: Shen Yuzhong Inventor after: Wu Chunzhong Inventor before: Qi Mingzhu Inventor before: Wang Dongchao Inventor before: Li Anmin Inventor before: He Hongjun Inventor before: Xiong Suyi Inventor before: Tang Dinglong Inventor before: Shen Yuzhong Inventor before: Wu Chunzhong |